Synthesis and Application of Cationic Softeners

Huseini Shabbir Patanwala* & V. A. Dorugade

Institute of Chemical Technology, Mumbai

Abstract
Esterquats which are quaternary ammonium compounds having two long (C16 C18) fatty acid chains with two
weak ester linkages, represent a new generation of fabric softening agents, having replaced the dialkyldimethyl
ammonium salts (ex. DTDMAC and DSDMAC). Inclusion of ester linkages into the aliphatic chains has significantly
improved the kinetics of biodegradation of the cationic surfactants, lowering the environmental exposure levels.
This new generation of fabric softening agents combines a good environmental profile with the structural features
required for an effective fabric conditioner. The basic drawback observed in cationic softeners is their yellowing
property. Work has been has done so as to reduce this yellowing property by carrying out the esterification reaction
in presence of nitrogen atmosphere.

Key words
Cationic softeners, textile conditioners, esterquats, triethanolamine, myristic acid, palmitic acid, stearic acid.

1.1. Cationic Softeners

Cationic surfactants have been defined as materials
which dissolve or disperse in water, concentrate and
orient at interfaces and ionize in such a way that the
cation includes a hydrocarbon chain, which is
hydrophobic and contains from 8 to 25 carbon atoms[2].
1.2. Interesting advantages[2]
Cationic compounds present some interesting advantages
as textile softeners. Because of their substantivity to
textile fibres they produce a more permanent softening
effect than either anionic or nonionic compounds.
Further, they are more effective as well, since they are
effective at much lower concentration.
The alkyl chain found to be most satisfactory in
softening is the saturated C18 chain (stearyl). Since it is
a saturated molecule there is minimum tendency of
yellowing. The compounds containing this chain are
*Correspondance should be addressed to,
Huseini Shabbir Patanwala
A/504, Kaif Towers, 40/44, Tank Bunder Road,
Reay Road, Mazgaon, Mumbai 400010, India
E-mail : [email protected]

more likely to produce cloudy colloidal dispersions than

compounds prepared with lauryl (C12) chain or with
unsaturated (oleyl) carbon chain. Dialkyl chain produces
a greater total softening effect and greater efficiency
per mole than the same type of compound containing
only one long chain.
Most of the cationic softeners show strong germicidal
properties. According to bacteriologists, those cationic
compounds with shorter alkyl chains or those having
unsaturation are better bactericides than those which
are usually preferred as textile softeners. The long,
saturated alkyl groups (C16H33 -, C18H37 -) are preferred
for softening, but they reduce water solubility. However,
when the amine is quaternised, increased solubility and
greater pH stability results. The anion may be chloride,
acetate, bromide, methosulphate, phosphate, lactate, etc.
In general, the structure and composition of the cation
determines the overall effect of the molecule and the
anion affects certain physical properties.
1.3. Types of Cationic Softeners[2]
(a) Mono-Amines and their salts: The simplest
cationics are the primary, secondary and tertiary monoamines and their salts, formed by neutralization of the
amines usually with acetic acid.
(b) Amido Amines: amido-amines are formed by the
reaction of a fatty acid or a glyceride (fat) and a
substituted or unsubstituted short chain polyamine.
R-COOH + H2N-CH2-CH2-N-(C2H5)2
CH2-N-(C2H5)2 + H2O
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R-CONH-CH2-

Journal of the TEXTILE Association

1. Introduction
Textile softeners are used to vary the handle of fabrics
(similar to filling, stiffening and weighing finishes).
They should demonstrate a positive effect on the handle
of treated textiles: many textiles require softer, smoother,
supple handle for the best sales potential. They may
also serve to improve the processability and wear
characteristics of the textiles[1].

(c) Imidazolines: Imidazolines are formed from fatty

acid and polyethylene polyamine.
(c) Aminoesters: are aminoesters prepared by reaction
of fatty acid or acid chloride with amino alcohols like
diethanolamine or hydroethyl ethylene diamine.
R-COOH + HO-CH2-CH2-NH-CH2-CH2-OH
CH2-CH2-NH-CH2-CH2-OH + H2O

R-COO-

R-COOH + HO-CH 2 -CH 2-NH-CH 2 -CH 2 -NH 2

RCOOCH2-CH2-NH-CH2-CH2-NH2 + H2O
(e) From dicyandiamide and stearyl amine: They are
prepared from dicyandiamide and stearyl amine
followed by reaction with ethylene oxide to impart water
solubility to the compound.
1.4. Application
There are two principal methods of application of
cationic softeners
1. Exhaustion from dilute baths
2. Padding from relatively concentrated solutions

Journal of the TEXTILE Association

The long bath (exhaustion) process is especially suitable

because of the natural substantivity of the softeners
and is usually adopted for knitted goods, not requiring
resin treatment. With thermosetting resins (urea
formaldehyde resin), cation lubricants/softeners are a
valuable adjunct to the treatment; since, they are not
appreciably removed in the subsequent washing
operation and serve to reduce needle cutting during
garment manufacture and generally impart improved
tear and abrasion resistance[2].
1.5. Esterquats[3]
Esterquats are one of the varieties of cationic surfactants.
Cationic surfactants are the main ingredients of fabric
softening formulations used worldwide. In 1977, esterquats
based on triethanolamine were patented for use as fabric
softeners. Some important features of esterquats are:
They can be formulated into high active dispersion
They do not cause fabric staining and pass
European environmental safety guidelines
They have hydrolytic stability and the softening
can be improved by adjusting dispersion pH to a
maximum of 4.
They meet test guidelines of the Organization for
Economic Corporation and Development (OECD).
v. Out of the various existing cationic molecules for
fabric softening, eaterquats are gaining superiority
because of their ecofriendly nature and excellent
biodegradability.
184

2. Materials and Experimental Methods

2.1. Materials Required
For Synthesis
CHEMICAL
2-propanol
Hypophosphorous
acid
Triethanolamine
Dimethyl sulphate
Glycine
Stearic acid
Myristic acid
Palmitic acid
Oleic acid
Zywet P 100

GRADE
For synthesis
30-32% LR

SOURCE
Merck Specialities Pvt. Ltd.
S.D. Fine Chemical Ltd.

LR
S.D. Fine Chemical Ltd.
LR
S.D. Fine Chemical Ltd.
(For synthesis)
LR
S.D. Fine Chemical Ltd.
90%
Godrej Industries Ltd.
99%
Godrej Industries Ltd.
Godrej Industries Ltd.
Rossari Biotech India Pvt. Ltd.
-

For Application 100% Cotton fabric; 100% Polyester

fabric; Acetic Acid was used.
For Testing Methylene Blue; Zywet P 100; Chloroform;
Bromophenol Blue; Hydrochloric acid and Ethanol
were used.
2.2. Experimental Methods
2.2.1. Synthesis of Softeners[4]
Seven different softeners were prepared by esterification
followed by quaternisation.
Esterification
0.32 moles of either A1, A2, A3, A4, A5, A6 or A7 and
0.1 mole of triethanolamine and 1ml of 30-32%
hypophosphorous acid were introduced into a 1 litre
three-necked flask equipped with a stirrer, nitrogen inlet,
internal thermometer and a distillation bridge. where,
A1 Myristic Acid; A2 Palmitic Acid; A3 Stearic
Acid; A4 Oleic Acid
A5 Myristic, Palmitic and Stearic Acid in the ratio
2:1:1
A6 - Myristic, Palmitic and Stearic Acid in the ratio
1:2:1
A7 - Myristic, Palmitic and Stearic Acid in the ratio
1:1:2
The reaction mixture was then heated to a temperature
of 160C for 4 hours. The crude acid triethanolamine
ester was then cooled. Air was then passed through the
reaction mixture with continuous stirring for 15 min.
Quaternisation
A mixture of 0.05 moles of ester from esterification
step in 75ml of isopropyl alcohol was introduced into
and heated with stirring to 45C in a 1 litre three necked
flask equipped with a stirrer, dropping funnel and reflux

Nomenclature
Softener 1 is obtained by esterification and
quaternisation of A1 i.e. Myristic Acid, Softener 2 is
the product of esterification and quaternisation of A2
i.e. Palmitic Acid, and so on and so forth, until finally
we have Softener 7 which is the esterified and
quaternized product of A7 i.e. Myristic, Palmitic and
Stearic Acid in the ratio 1:1:2
2.2.2. Application
The finish was applied by pad-dry-cure technique.
However before application emulsions of the
corresponding esterquats were prepared as per the
following recipe
Esterquat
Zywet P 100
Isopropyl alcohol
Water

20%
5%
2%
Rest

The finish bath was prepared as per the following recipe

Esterquat emulsion
Acetic acid

15gpl
2gpl

The fabric was padded through above solution with

70% expression using 2dip2nip method. Cotton fabric
was then dried at 80C for 2 mins. followed by curing
at 150C for 5 mins. whereas polyester fabric was dried
at 80C for 2 mins. followed by curing at 180C for
1 min.
2.2.3. Testing
2.2.3.1. Methods for analysis of esterquat (ionic
nature)[5]
(a) Methylene blue test
First add 2 drops of a known anionic surfactant
(Zywet P 100) was added to a mixture of 5ml
methylene blue solution and 5ml of chloroform &
shaken well and left to stand until the chloroform
layer shows a blue. Then a few drops of sample
solution was shake added well and left for layers
to form. If the blue color in the chloroform layer
becomes lighter or colorless, the existence of
cationic surfactant in the sample can be confirmed.

(b) Bromophenol blue test

Bromophenol blue solution was prepared by
addition of 20ml of 0.1% bromophenol blue in
96% ethanol to a mixture of 75ml 0.2N sodium
acetate and 925ml 0.2N acetic acid. The pH of
the solution was adjusted to 3.6-3.9.
i. For the test, 2-5drops of a neutralized sample
solution was added to 10ml of bromophenol
blue solution, shaken well and the color of
the mixture observed. If a blue color is shown,
existence of a cationic surfactant is confirmed.
ii. Alternately, 1 drop of 5% sample solution
was added to a mixture of 5ml chloroform,
5ml of 0.1% bromophenol blue dilute ethanol
solution and 1 ml 6N HCl, shaken well and
the color of the chloroform layer observed. If
a yellow color appears, there is a cationic
surfactant in the sample.
2.2.3. Methods for analysis of treated fabric
(a) Assessment of bending length was
IS: 6490-1971 was used to measure Stiffness of
fabrics. Results are expressed in bending length
(to calculate flexural rigidity) and bending modulus
of fabrics.
(b) Assessment of fabric drape
IS: 8357 1977 was used to measure the drape
coefficient of fabrics.
(c) Method of assessment of whiteness and yellowness
index
2
Cut the test specimens in 10 X 5 cm , from the
fabric to be tested. In cutting the specimens,
selvedges, end pieces, and creased or folded places
shall be avoided, and specimens should be handled
as little as possible. The specimens are cut and
the whiteness and yellowness index are measured
for the unexposed specimens. For this purpose
Datacolor Tools were used to measure the CIE
Whiteness Index and D1925 Yellowness Index.
The specimens were then allowed to be exposed
to D65 light for 8 hours & again the whiteness
index and yellowness index is measured.
3. Results and Discussions
3.1. Ionic nature
a. Methylene blue test:
Blue color in the chloroform layer becomes lighter
b. Bromophenol blue test:
i. Mixture of sample and bromophenol blue
solution shows a blue coloration.
ii. Chloroform layer shows yellow coloration
185

Journal of the TEXTILE Association

condenser. 0.049 moles of dimethyl sulphate were added

dropwise over a period of 2 hours. After the addition,
the mixture was stirred for another 2 hours at 60C.
The solvent was removed via distillation and unreacted
dimethyl sulphate was destroyed by addition of 0.001
mole of glycine.

3.2. Bending length

Graph 3.1 & 3.2: Bending length of cotton samples

Graph 3.6: Drape coefficient of Polyester Samples

Graph 3.7 & 3.8: Whitness & Yellowness index for Cotton samples

Journal of the TEXTILE Association

Graph 3.3 & 3.4: Bending length of polyester samples

Graph 3.9 & 3.10: Whitness & Yellowness index for Polyster samples

Graph 3.5: Drape coefficient of Cotton Samples

186

3.10, i.e., the whiteness index of the blank and treated

fabric reduces after exposure, whereas the yellowness
index increases on exposure with D65 light. Here we
can see that, softener 3 shows minimum yellowing
tendency, whereas softener 7 shows higher yellowing
tendency. However the changes in the whiteness and
yellowness index observed are more pronounced for
cotton fabric as compared to polyester fabric. Hence,
there is a higher tendency of yellowing observed in
cotton as compared to polyester.

Graph 3.5 and 3.6 also follow a similar trend. The

treated specimen shows a decrease in the drape
coefficient, much more prominent in case of 100%
cotton when compared with 100% polyester. Softener
7, a mix of myristic, palmitic and stearic acid in the
ratio 1:1:2 gives the best draping effect.
Graph 3.7 and Graph 3.6 indicates that the whiteness
index of the treated specimen reduces after exposure,
whereas, the yellowness index increases on exposure
with D65 light. Here it can be seen that softener 3
gives higher difference in the whiteness and
yellowness index, in other words gives higher
yellowing property. Also it can be seen that softener
7 shows lowest yellowing tendency.

References
1. Hans-Karl Rouette, Encyclopedia of Textile Finishing,
Springer Publications, Vol. 3, p. 2114-2118 (2001).
2. V. A. Shenai, Technology of Textile Processing, Sevak
Publications, Vol. 5, p. 305-313 (2002).
3.
Rashmi Tyagi, V. K. Tyagi and R. K. Khanna,
Synthesis, Characterisation and Performance of Tallow
Fatty Acids and Triethanolamine based Esterquats,
Journal of Oleo Science, Vol. 55, No. 7, p. 337-345
(2006).
4. Nuria Bonastre, Barbara del Valles, Joaquim Bigorra
Llosas, Sabadell, Rafael Pi Subirana, Granollers, U.
S. Patent, 5 886 201 (1999).
5. Qinguo Fan, Chemical testing of textiles, Woodhead
Publications, p. 72 (2005).

Similar effects are observed for Graph 3.9 and Graph

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Journal of the TEXTILE Association

From the ionic nature tests conducted it can be said

that the esterquats are cationic in nature. Graph 3.1,
3.2, 3.3, and 3.4 shows significant decrease in
bending length as compared to the blank specimen.
A more prominent effect is observed in case of 100%
cotton. Softeners 3, 6 and 7 provide better softening
and hence a lower value of bending length.

4. Conclusion
Cationic softeners are preferred as compared to
anionic and nonionic softeners owing to their
substantivity towards textile fibres. Cationic softeners
can be applied to both, natural and synthetic fibres /
fabric. However they show a tendency of yellowing.
The above softener compositions were found to be
better for 100% cotton as compared to 100%
polyester. On comparing softener 3 and softener 4,
i.e., the one made from stearic acid and oleic acid
respectively, softener 3 gave better softness property.
Following the trends, it can be concluded that the
saturated fatty acids are more efficient for softening
when compared to unsaturated fatty acids (oleic acid
in this case). Also, longer the saturated fatty acid
chain better is the effect. In case of myristic, palmitic
and stearic acid mixtures, the softener with the three
acids in the ratio 1:1:2 i.e. softener 7 gives better
results when compared to softener 5 and 6. Hence,
it can be concluded that they work synergistically.
Also, of the seven softeners prepared, softener 3 and
softener 7 depict best results when compared to
others.